EP1026178B1 - Maleic anhydride copolymers containing amine oxide groups and use thereof as dispersants for pigments and fillers - Google Patents

Abstract

Amine oxide group-containing maleic anhydride copolymers, obtained by reacting at least 1 mol% of the anhydride groups with a primary/tertiary diamine and then oxidizing the tertiary amino groups to form amine oxide groups attached to the polymer chain by half-amide and/or imide groups. Amine oxide group-containing maleic anhydride (MA) copolymers, obtained by (a) reaction of at least 1 mol% of the anhydride groups in MA copolymers with diamines of formula (I), followed by (b) oxidation to form amine oxide groups attached by half-amide and/or imide groups of formula (II) and/or (III). R<1> = H or 1-24C hydrocarbyl; R<2> = 2-24C alkylene; R<3>, R<4> = 1-12C (preferably 1-6C) aliphatic and/or alicyclic alkyl groups.

Description

The present invention relates to amine oxide groups Maleic anhydride copolymers and their use as dispersants for pigments or fillers

According to the prior art are used as dispersants often polyacrylic acid esters with acidic and / or basic Groups used, which can also be salted, which by polymerization of corresponding monomeric acrylic acid esters, such as butyl acrylate, acrylic acid, 2-hydroxyethyl acrylate and its alkoxylation products and other monomers with vinyl double bonds such as Example styrene or vinylimidazole can be produced (see for example EP-B-0 311 157). There are but also descriptions, such as by transesterification reactions on polyacrylic acid alkyl esters by exchanging the alkyl group in the sense of a polymer-analogous reaction using alcohols or amines such dispersants can be produced (see for example EP-B-0 595 129, DE-C-39 06 702, EP-A-0 879 860). Advantages of polymer-analogous reaction control are said to have a narrower molecular weight distribution and a Freedom from disturbing or toxic monomer components lie. In addition, it should be possible to produce polymers due to direct polymerization due to lack of technical availability corresponding polymerizable monomers are not are accessible. Such alcoholysis or aminolysis require often the use of strongly acidic catalysts as a rule such as sulfuric acid or paratoluenesulfonic acid or metal salts such as titanates, the at the specified reaction temperatures of up to 200 ° C in addition to undesirable side reactions, the molecular weight build-up provoke, also often produce strongly colored products, because of their coloring for demanding Dispersing tasks not or only poorly suited are.

The same is true for polymers, the diesters are radical polymerizable dicarboxylic acids, such as Maleic dialkyl esters, included, as a basis for production of dispersants, such as this is stated in WO 96/14347. First there is a transesterification of the dicarboxylic acid alkyl ester with a hydroxy-functional Polyoxyalkylene described, followed by one subsequent copolymerization with another vinyl unsaturated monomer. It is also disadvantageous here that the transesterification step, preferably acidic in the presence Catalysts, reaction temperatures of approx. 160 ° C required, which also related the disadvantages mentioned above on the usability of the dispersants obtained in this way entail. The subsequent copolymerization is more expensive, more organic at high dosages Peroxides are instructed as sufficient initiators Get sales and reproducible copolymers. in the The rule remains, especially when using Monomers with weight average molecular weight larger 500 g / mol considerable proportions of unpolymerized monomer in the Reaction mixture unreacted, which no longer can be removed economically. In addition to economic Disadvantages are particularly due to the potential toxic properties that are radically polymerizable Vinyl compounds mostly inherent, undesirable. Moreover the products are usually after the copolymerization darkened again strongly. This limits possible ones Areas of application in turn to a large extent.

With the above-described, according to the prior art Dispersants can also be used in a wide variety of applications Requirements particularly in the area high quality industrial coatings, such as the Automobile series painting, not or not 'in full be fulfilled. So sometimes prevent again and again mutually dependent disadvantages, such as lack of compatibility with various binders, sufficient Efficacy only at very high doses of Dispersant, dispersing times too long, too short achievable pigmentation levels, insufficient color strength development, Viscosity and color constancy (especially after storage) or flocculation and aggregation (also delayed) due to weak stabilization of the Pigments due to the dispersant their wide use.

The present invention is therefore based on the object overcome a number of the disadvantages mentioned and to provide new dispersants that are easily manufactured can be and in particular by extraordinary distinguish good application properties.

Surprisingly, it was found that the prior art superior new dispersants can be obtained that do not have the disadvantages mentioned above.

a) Diaminen aus der Gruppe HR¹N-R²-NR³R⁴    wobei

R¹

ein Wasserstoffrest oder ein einwertiger Kohlenwasserstoffrest mit 1 bis 24 Kohlenstoffatomen ist,

R²

ein zweiwertiger Alkylenrest mit 2 bis 24 Kohlenstoffatomen ist und

R³ und R⁴

aliphatische und/oder alicyclische Alkylreste mit 1 bis 12, bevorzugt 1 bis 6 Kohlenstoffatomen sind, die gleich oder verschieden sein können

umsetzt und anschließend zu Aminoxidgruppen der allgemeinen Formel (wie dem Fachmann geläufig, sollen die Wellenlinien andeuten, daß es sich hier und im folgenden bei dieser Darstellung lediglich um einen Ausschnitt einer polymeren Verbindung handelt)

oxidiert, die restlichen Anhydridgruppen ganz oder teilweise mit

b) gesättigten oder ungesättigten, alicyclischen oder cyclischen Alkoholen und/oder Aminen der allgemeinen Formel HO-R¹ bzw. HR²N-R¹    wobei

R¹

ein Kohlenwasserstoffrest mit 2 bis 24 Kohlenstoffatomen ist und

R²

ein Wasserstoffrest oder ein einwertiger Kohlenwasserstoffrest mit 1 bis 24 Kohlenstoffatomen ist

und/oder

c) Polyoxyalkylenverbindungen der allgemeinen Formel H- (O-C₂H_4-aR³ _a)_b(O-C_cH_2c)_dO-R⁴,    wobei

R³

gleiche oder verschiedene Alkylreste oder Alkylenreste mit 1..bis 24 Kohlenstoffatomen oder, gegebenenfalls substituierte, Phenylreste mit bis zu 24 Kohlenstoffatomen sind und

R⁴

ein Wasserstoffrest oder ein gesättigter oder ungesättigter, gegebenenfalls verzweigter oder cyclischer oder aromatischer Kohlenwasserstoffrest mit bis zu 24 Kohlenstoffatomen ist, der gegebenenfalls auch Heteroatome aus der Gruppe O, S, N, P, Si, F, Cl, Br, und I enthalten kann,

a = 0 bis 3,
b = 0 bis 100,
c = 2 bis 12,
d = 0 bis 100,
und die Summe (b + d) = 2 bis 200 ist,
   wobei die Reihenfolge der Polyoxyalkylensegmente
(O-C₂H_4-aR³ _a)_b und (O-C_cH_2c)_d beliebig ist
und/oder

d) Polyoxyalkylenverbindungen der allgemeinen Formel H₂N-R⁵-(O-C₂H_4-aR³ _a)_b(O-C_cH_2c)_dO-R⁶,

   wobei

R³

gleiche oder verschiedene Alkylreste oder Alkylenreste mit 1 bis 24 Kohlenstoffatomen oder, gegebenenfalls substituierte, Phenylreste mit bis zu 24 Kohlenstoffatomen sind,

R⁵

ein zweiwertiger Alkylenrest mit 2 bis 6 Kohlenstoffatomen ist und

R⁶

ein Wasserstoffrest oder ein gesättigter oder ungesättigter, gegebenenfalls verzweigter oder cyclischer oder aromatischer Kohlenwasserstoffrest mit bis zu 24 Kohlenstoffatomen ist, der gegebenenfalls auch Heteroatome aus der Gruppe O, S, N, P, Si, F, Cl, Br, und I enthalten kann,

a = 0 bis 3,
b = 0 bis 100,
c = 2 bis 12,
d = 0 bis 100,
und die Summe (b + d) = 2 bis 200 ist,
   wobei die Reihenfolge der Polyoxyalkylensegmente (O-C₂H_4-aR³ _a)_b und (O-C_cH_2c)_d beliebig ist umsetzt.These are maleic anhydride copolymers containing amine oxide groups, which can be obtained by adding at least 1 mol% of the anhydride groups of maleic anhydride copolymers

a) diamines from the group HR ¹ NR ² -NR ³ R ⁴ in which

R ¹

is a hydrogen radical or a monovalent hydrocarbon radical with 1 to 24 carbon atoms,

R ²

is a divalent alkylene radical having 2 to 24 carbon atoms and

R ³ and R ⁴

are aliphatic and / or alicyclic alkyl radicals having 1 to 12, preferably 1 to 6, carbon atoms, which may be the same or different

and then to amine oxide groups of the general formula (as is known to the person skilled in the art, the wavy lines are intended to indicate that here and in the following this representation is merely a section of a polymeric compound)

oxidized, the remaining anhydride groups in whole or in part

b) saturated or unsaturated, alicyclic or cyclic alcohols and / or amines of the general formula HO-R ¹ or HR ² NR ¹ in which

R ¹

is a hydrocarbon radical having 2 to 24 carbon atoms and

R ²

is a hydrogen radical or a monovalent hydrocarbon radical having 1 to 24 carbon atoms

and or

c) polyoxyalkylene compounds of the general formula H- (OC ₂ H _4-a R ³ _a ) _b (OC _c H _2c ) _d OR ⁴ , in which

R ³

are identical or different alkyl radicals or alkylene radicals with 1 to 24 carbon atoms or, optionally substituted, phenyl radicals with up to 24 carbon atoms and

R ⁴

is a hydrogen radical or a saturated or unsaturated, optionally branched or cyclic or aromatic hydrocarbon radical with up to 24 carbon atoms, which may optionally also contain heteroatoms from the group O, S, N, P, Si, F, Cl, Br, and I,

a = 0 to 3,
b = 0 to 100,
c = 2 to 12,
d = 0 to 100,
and the sum (b + d) = 2 to 200,
the order of the polyoxyalkylene segments
(OC ₂ H _4-a R ³ _a ) _b and (OC _c H _2c ) _{d is} arbitrary
and or

d) polyoxyalkylene compounds of the general formula H ₂ NR ⁵ - (OC ₂ H _4-a R ³ _a ) _b (OC _c H _2c ) _d OR ⁶ ,

in which

R ³

are identical or different alkyl radicals or alkylene radicals having 1 to 24 carbon atoms or, optionally substituted, phenyl radicals having up to 24 carbon atoms,

R ⁵

is a divalent alkylene radical having 2 to 6 carbon atoms and

R ⁶

is a hydrogen radical or a saturated or unsaturated, optionally branched or cyclic or aromatic hydrocarbon radical with up to 24 carbon atoms, which may optionally also contain heteroatoms from the group O, S, N, P, Si, F, Cl, Br, and I,

a = 0 to 3,
b = 0 to 100,
c = 2 to 12,
d = 0 to 100,
and the sum (b + d) = 2 to 200,
the order of the polyoxyalkylene segments (OC ₂ H ₄ -a R ³ _a ) _b and (OC _c H _2c ) _{d is} arbitrary.

The index a can be different in a polyoxyalkylene Accept values. This is to express that suitable Polyoxyalkylenes both for example homopolymers of Ethylene glycol, copolymers of ethylene glycol and 1,2-propylene glycol, but also a multiple copolymer of more than two monomers, such as ethylene glycol, 1,2-propylene glycol and 1,2-butylene glycol. Independently the index c in a polyoxyalkylene can also differ from these Accept values so that, for example, multiple copolymers additionally be constructed with 1,4-butylene glycol can and the copolymers randomly or in blocks can be built.

The maleic anhydride copolymers containing amine oxide groups according to the invention can at least as a comonomer another different monomer with vinyl double bonds, preferably a monomer from the group styrene, alkylated styrene compounds, (meth) acrylic acid, (meth) acrylic acid ester, Alkyl vinyl ether, vinyl acetate, itaconic acid ester or mixtures of monomers from this group contain.

Styrene is preferably used as comonomer, the molar ratio of maleic anhydride to styrene between 1 to 1 and 1 to 3.

The maleic anhydride copolymers containing amine oxide groups according to the invention preferably have a molecular weight M _{w of} from 1000 to 10,000, preferably from 2500 to 50,000 g / mol.

Depending on the desired properties, those in the polymer existing carboxylic acid groups neutralized to carboxylate salts become.

Another object of the invention is the use of the maleic anhydride copolymers containing amine oxide groups as a dispersant for pigments or fillers, especially for the production of pigment concentrates, wherein the dispersant together with those to be dispersed Pigments and / or fillers, optionally in the presence of organic solvents and / or water, if appropriate with binders and, if necessary, with customary paint auxiliaries is homogenized.

The invention also relates to the use of copolymers according to the invention for producing a coating composition, where a binder, optionally a solvent, Pigments and / or fillers, the dispersant and optionally auxiliaries dispersed together become.

A novel class of dispersing additives is thus in accordance with the invention with unexpectedly outstanding properties provided.

To illustrate the course of the reaction and the resulting structures, the following formula scheme can be seen as an example:

It is known to the person skilled in the art that, of course, through the use of compounds that are more than just nucleophilic Functional substitution enabled functional groups Contain group, such as di- or trihydroxy compounds by intermolecular reaction on two or more Anhydride groups, i.e. different maleic anhydride copolymers are associated with a molecular weight build-up by a crosslinking reaction between at least two Maleic anhydride copolymer chains can be done. This you can take advantage of and through the amount the molecular weight of the added multifunctional compound control the entire molecule within wide limits, all the more special properties, such as viscosity, targeted adjustment.

The dispersing properties which have long been known to the person skilled in the art of maleic anhydride copolymers and their derivatives obtainable by alcoholysis or aminolysis, such as for example in JP 62 183 845, WO 97/15382 and EP-0 747 457 can be described by Introduction via half-amide and / or imide groups Amine oxide groups can be significantly improved. This too while maintaining the original variety of structural Possible variations of the maleic anhydride copolymers, which, as is known to the person skilled in the art, by reaction with different nucleophiles, the ones mentioned at the beginning Alcoholysis or aminolysis products of acrylic acid alkyl ester polymers at least equal in their diversity are, but significant advantages in terms of application technology Offer.

That a comparatively minor modification of the Maleic anhydride copolymers from 1 mol% per anhydride group with bound via half amide and / or imide groups Amine oxide groups of the general formula given above a significant improvement in the dispersing properties is surprising, since the dispersion promoting property of amine oxides for pigments or Fillers is hardly known. This shows that amine oxides are obviously particularly well qualified with various Interaction of pigment surfaces and thus for the most reliable adsorption of the dispersant to care for on the pigment surface. amine oxides thus act as particularly effective, so-called "Anchor groups", such as for carboxylic acid groups has also been described quantitatively for a long time (see for comparison L. Dintenfass, JOCCA, 41 (1958) 125); an overview of other anchor groups, the different ones Mechanisms and further literature can be found in J.D. Schofield, Polymeric Dispersants, in Handbook of coatings additives, Vol. 2, 1st edition (L.J.I. Calbo, Ed.), Marcel Dekker, New York (1992) 71.

However, amine oxides themselves are according to the prior art usually only in the form of or in combination with betaine compounds (so-called "inner salts") as a dispersion promoting agent as described in JP 63 095 277 (for aluminum in printing inks), US-A-4 486 405 (for metal oxides in cosmetic formulations), DE-B-25 46 810 (for fillers in epoxy systems) and DE-B-16 44 193 (post-treatment of azo dyes) becomes.

The maleic anhydride copolymers used as the basic raw material are commercially available (Leuna-Harze GmbH, D-06236 Leuna) or can be customary according to the state of the art Methods by radical polymerization of maleic anhydride with at least 100 mol% of another different Monomers with vinyl double bonds, preferably a monomer from the group styrene, alkylated Styrene compounds, (meth) acrylic acid, (meth) acrylic acid ester, Alkyl vinyl ether, vinyl acetate, itaconic acid ester or Mixtures of monomers from this group easily obtained become. Styrene is particularly suitable as a comonomer if the molar ratio of maleic anhydride to styrene between 1 to 1 and 1 to 3. Such copolymers are intensive since the 1940s has been researched and has been continuous since then has been studied, such as S.D. Baruah, N.C. Laskar, J. Appl. Polym. Sci. (1996), 60, 649 and US-A-4 180 637 show.

The reaction of the anhydride groups with the amino and / or hydroxy compounds listed can be carried out either with the addition of solvents and catalysts or without additional solvents and catalysts. In individual cases, however, the use of basic catalysts such as tertiary amines with low nucleophilicity is advantageous. Depending on the selected temperature and particularly advantageously using a temperature gradient, the preferred formation of half-amides and imides can be set, the half-amides (addition reaction) already forming at room temperature, while for the synthesis of the imides (condensation reaction), depending on the reaction component, solvent and experimental setup preferably temperatures from 80 ° C are necessary:

The amine oxides according to the invention can then be prepared by processes known from the literature by simple oxidation with aqueous hydrogen peroxide solution at moderate temperatures. The other structural elements or functional groups contained in the molecule according to the invention are not impaired. The reaction is shown below using an example of a maleimide derivative according to the invention:

It is known to the person skilled in the art that, depending on the reaction conditions likewise in the presence of water, at least partially, the analogous amine oxide hydrates of the invention Amine oxides can be formed. Their possible occurrence in the dispersants of the invention therefore no further special mention and is with the use of the term "amine oxide" is therefore sufficient made clear and described.

Preparation Examples General manufacturing instructions

A maleic anhydride copolymer (copolymer of maleic anhydride and styrene; from Leuna Harze GmbH) with an acid number of 335 mg KOH / g and a molecular weight average of M _w = 10,000 to 20,000 g / mol is mixed in a methyl ethyl ketone / methyl isobutyl ketone mixture ( Mixing ratio 20 to 80 wt .-%) dissolved and with a mixture of a monohydroxy-functional polyoxyalkylene (copolymer of ethylene oxide and propylene oxide with 25 wt .-% propylene oxide, hydroxyl number 34 mg KOH / g, viscosity 300 mPas / 25 ° C), an amino-functional Polyoxyalkylene (Jeffamin M 2070; Texaco Chemical Company) and with N, N-dimethylaminopropylamine in the desired molar ratio, based on the anhydride groups of the maleic anhydride copolymer. This mixture is heated under pressure for 4 hours. At a desired acid number of the resulting product, the reaction is stopped. The solvent is removed by distillation. A light yellow, medium-viscosity, clear liquid is obtained.

40 g of the light yellow, medium-viscosity reaction product thus obtained are diluted with 60 g of water, with 0.1% by weight of ethylenediaminetetraacetate (EDTA) and added Heated to 70 ° C. After adding 1.5 g of 30% aqueous hydrogen peroxide solution is stirred for 8 hours. Subsequently is heated to 100 ° C and excess. Peroxide in Overcooked for 4 hours.

The end product is also light yellow, low viscosity and clear.

The following 8 production examples were produced in accordance with this specification. Production examples 1 to 5 were synthesized according to the invention according to the instructions given, with the formation of amine oxide groups bonded via half-amide and / or imide groups. In contrast, in preparation examples 6 to 8 (not according to the invention) no amine oxide groups bonded via half-amide and / or imide groups were formed. Preparation example Monohydroxy-functional polyoxyalkylene [mol%] Jeffamin M 2070 [mol%] N, N-dimethylaminopropylamine [mol%] Reaction temperature [° C] Acid number at the end of the reaction [mg KOH / g] 1 20 10 10 150 65 2 40 0 15 150 47 3 10 20 20 150 48 4 20 20 10 150 44 5 25 25 5 150 36 6 50 0 0 135 63 7 0 50 0 150 32 8th 25 25 0 150 39

applications

To produce aqueous pigment pastes, 0.1 to 100% by weight of the maleic anhydride copolymers according to the invention, preferably 0.5 to 50% by weight (based on the weight of the pigments). The copolymers according to the invention can either be dispersed in advance Pigments are mixed or directly the dispersing medium (Water, possible glycol ether additives) before or at the same time with the addition of the pigments and any other Solids are solved.

Aqueous, highly concentrated, pumpable and flowable pigment preparations are easy to manufacture by that the polymer to be used, optionally in combination with at least one other component, with water mixed, the pigment in this mixture with stirring sprinkles and until the desired fineness is achieved and consistency of the suspension dispersed.

Another method of making the pigment preparations consists of a pigment with the invention First mix copolymers dry, from which a powdered pigment preparation results. This can be done at Need to be dispersed in water, the invention Pigment preparation is obtained.

A third method of making aqueous, highly concentrated, pumpable and flowable pigment suspensions and - paste consists of an aqueous-moist pigment filter cake to mix with the copolymer of the invention and for example with a dissolver in the pigment filter cake to incorporate, which liquefies.

- Monoazopigmente:

C.I. Pigment Brown 25;
C.I. Pigment Orange 5, 36 und 67;
C.I. Pigment Red 1, 2 ,3 ,48:4, 49, 52:2, 53, 57:1, 251, 112, 170 und 184;
C.I. Pigment Yellow 1, 3, 73, 74, 65, 97, 151 und 183;

- Diazopigmente:

C.I. Pigment Orange 34;
C.I. Pigment Red 144 und 166
C.I. Pigment Yellow 12, 13, 17, 83, 113 und 126;

- Anthrachinonpigmente:

C.I. Pigment Yellow 147 und 177;
C.I. Pigment Violet 31;

- Anthrapyrimidinpigmente:

C.I. Pigment Yellow 108;

- Chinacridonpigmente:

C.I. Pigment Red 122, 202 und 20;
C.I. Pigment Violet 19;

- Chinophthalonpigmente:

C.I. Pigment Yellow 138;

- Dioxazinpigmente:

C.I. Pigment Violet 23 und 27;

- Flavanthronpigmente:

C.I. Pigment Yellow 24;

- Indanthronpigmente:

C.I. Pigment Blue 60 und 64;

- Isoindolinpigmente:

C.I. Pigment Orange 69;
C.I. Pigment Red 260;
C.I. Pigment Yellow 139;

- Isoindolinonpigmente:

C.I. Pigment Orange 61;
C.I. Pigment Red 257 und 260;
C.I. Pigment Yellow 109, 110, 173 und 185;

- Metallkomplexpigmente:

C.I. Pigment Yellow 117 und 153;

- Perinonpigmente:

C.I. Pigment Orange 43;
C.I. Pigment Red 194;

- Perylenpigmente:

C.I. Pigment Black 31 und 32;
C.I. Pigment Red 123, 149, 178, 179, 190 und 224;
C.I. Pigment Violet 29;

- Phtalocyaninpigmente:

C.I. Pigment Blue 15, 15:1, 15:2,15:3, 15:4, 15:6 und 16;
C.I. Pigment Green 7 und 36;

- Pyranthronpigmente:

C.I. Pigment Orange 51;
C.I. Pigment Red 216;

- Thioindigopigmente:

C.I. Pigment Red 88;

- Triphenylmethanpigmente:

C.I. Pigment Blue 1, 61 und 62;
C.I. Pigment Green 1;
C.I. Pigment Red 81 und 169;
C.I. Pigment Violet 2 und 3;

• C.I. Pigment Black 1 (Anilinschwarz)
• C.I. Pigment Yellow 101 (Aldazingelb)

Examples of pigments to be dispersed are:

- monoazo pigments:

CI Pigment Brown 25;
CI Pigment Orange 5, 36 and 67;
CI Pigment Red 1, 2, 3, 48: 4, 49, 52: 2, 53, 57: 1, 251, 112, 170 and 184;
CI Pigment Yellow 1, 3, 73, 74, 65, 97, 151 and 183;

- diazo pigments:

CI Pigment Orange 34;
CI Pigment Red 144 and 166
CI Pigment Yellow 12, 13, 17, 83, 113 and 126;

- Anthraquinone pigments:

CI Pigment Yellow 147 and 177;
CI Pigment Violet 31;

- anthrapyrimidine pigments:

CI Pigment Yellow 108;

- Quinacridone pigments:

CI Pigment Red 122, 202 and 20;
CI Pigment Violet 19;

- Quinophthalone pigments:

CI Pigment Yellow 138;

- Dioxazine pigments:

CI Pigment Violet 23 and 27;

- Flavanthrone pigments:

CI Pigment Yellow 24;

- Indanthrone pigments:

CI Pigment Blue 60 and 64;

- Isoindoline pigments:

CI Pigment Orange 69;
CI Pigment Red 260;
CI Pigment Yellow 139;

- Isoindolinone pigments:

CI Pigment Orange 61;
CI Pigment Red 257 and 260;
CI Pigment Yellow 109, 110, 173 and 185;

- Metal complex pigments:

CI Pigment Yellow 117 and 153;

- Perinone pigments:

CI Pigment Orange 43;
CI Pigment Red 194;

- Perylene pigments:

CI Pigment Black 31 and 32;
CI Pigment Red 123, 149, 178, 179, 190 and 224;
CI Pigment Violet 29;

- phthalocyanine pigments:

CI Pigment Blue 15, 15: 1, 15: 2.15: 3, 15: 4, 15: 6 and 16;
CI Pigment Green 7 and 36;

- Pyranthrone pigments:

CI Pigment Orange 51;
CI Pigment Red 216;

- Thioindigo pigments:

CI Pigment Red 88;

- Triphenylmethane pigments:

CI Pigment Blue 1, 61 and 62;
CI Pigment Green 1;
CI Pigment Red 81 and 169;
CI Pigment Violet 2 and 3;

• CI Pigment Black 1 (aniline black)
• CI Pigment Yellow 101 (Aldazine Yellow)

- Weißpigmente:

Titandioxid (C.I. Pigment White 6), Zinkweiß, Farbenzinkoxid; Zinksulfid, Lithopone; Bleiweiß;

Schwarzpigmente :

Eisenoxidschwarz (C.I. Pigment Black 11), Eisen-Mangan-Schwarz, Spinellschwarz (C.I. Pigment Black 27); Ruß (C.I. Pigment Black 7);

- Buntpigmente:

Chromoxid, Chromoxidhydratgrün; Chromgrün (C.I. Pigment Green 48); Cobaltgrün (C.I. Pigment Green 50); Ultramaringrün; Kobaltblau (C.I. Pigment Blue 28 und 36); Ultramarinblau; Eisenblau (C.I. Pigment Blue 27); Manganblau;
Ultramarinviolett; Kobalt- und Manganviolett;
Eisenoxidrot (C.I. Pigment Red 101); Cadmiumsulfoselenid (C.I. Pigment Red 108); Molybdatrot (C.I. Pigment Red 104); Ultramarinrot;
Eisenoxidbraun, Mischbraun, Spinell- und Korundphasen (C.I. Pigment Brown 24, 29 und 31); Chromorange;
Eisenoxidgelb (C.I. Pigment Yellow 42); Nickeltitangelb (C.I. Pigment Yellow 53; C.I. Pigment Yellow 157 und 164); Chromtitangelb, Cadmiumsulfid und Cadmiumzinksulfid, (C.I. Pigment Yellow 37 und 35); Chromgelb (C.I. Pigment Yellow 34), Zinkgelb, Erdalkalichromate, Neapelgelb, Bismutvanadat (C.I. Pigment Yellow 184);

- Glanzpigmente:

Metalleffektpigmente auf Basis metalloxidbeschichteter Metallplättchen; Perlglanzpigmente auf der Basis metalloxidbeschichteter Glimmerplättchen.

Inorganic pigments:

- white pigments:

Titanium dioxide (CI Pigment White 6), zinc white, colored zinc oxide; Zinc sulfide, lithopone; White lead;

Black pigments:

Iron oxide black (CI Pigment Black 11), iron-manganese black, spinel black (CI Pigment Black 27); Carbon black (CI Pigment Black 7);

- Colored pigments:

Chromium oxide, chromium oxide hydrate green; Chrome green (CI Pigment Green 48); Cobalt green (CI Pigment Green 50); Ultramarine green; Cobalt blue (CI Pigment Blue 28 and 36); Ultramarine blue; Iron blue (CI Pigment Blue 27); Manganese blue;
Ultramarine violet; Cobalt and manganese violet;
Iron oxide red (CI Pigment Red 101); Cadmium sulfoselenide (CI Pigment Red 108); Molybdate red (CI Pigment Red 104); ultramarine;
Iron oxide brown, mixed brown, spinel and corundum phases (CI Pigment Brown 24, 29 and 31); Chrome orange;
Iron oxide yellow (CI Pigment Yellow 42); Nickel titanium yellow (CI Pigment Yellow 53; CI Pigment Yellow 157 and 164); Chromium titanium yellow, cadmium sulfide and cadmium zinc sulfide, (CI Pigment Yellow 37 and 35); Chrome yellow (CI Pigment Yellow 34), zinc yellow, alkaline earth metal chromates, Naples yellow, bismuth vanadate (CI Pigment Yellow 184);

- gloss pigments:

Metallic effect pigments based on metal oxide coated metal flakes; Pearlescent pigments based on mica flakes coated with metal oxide.

Fillers, for example dispersed in aqueous paints can be z. B. those based on Kaolin, talc, other silicates, chalk, glass fibers, Glass beads or metal powders.

As coating systems in which the pigment preparations according to the invention can be lacquered, come any aqueous 1K or 2K paints into consideration. Named as an example be aqueous IK lacquers, such as those based on of alkyd, acrylate, epoxy, polyvinyl acetate, polyester or polyurethane resins, or aqueous 2-component paints, for example those based on hydroxyl-containing polyacrylate or polyester resins with melamine resins or optionally blocked polyisocyanate resins as crosslinkers. Polyepoxy resin systems may also be mentioned in the same way.

Water is the preferred solvent for the invention Copolymers. But also organic solvents, such as Glycol ether or ester, alone or in Mixture with water can be used. Especially for that Drying behavior of the copolymers according to the invention The pigment pastes produced are the addition of solvents often advantageous.

Can be used to produce the pigment pastes according to the invention also the addition of other non-inventive, water-dispersible Polymers such as polyacrylate, Polyurethane or polysiloxane derivatives take place.

In the production of the pigment concentrates according to the invention can also contain other auxiliaries, such as defoamers, preservatives, Wetting agent, deaerator or the State-of-the-art anti-settling agents, Waxes or rheology additives are used.

Production of pigment pastes

To produce the pigment pastes, the inventive (1 to 5) and non-inventive (6 to 8) Dispersing additives, 40% pre-dissolved in water, with water and auxiliaries mixed and then added the pigments. The dispersion takes place after the addition of grinding media (Glass balls 2 to 3 mm, same volume as the pigment paste) 1 (titanium dioxide) or 2 h (other pigments) in one Skandex vibrator with air cooling.

Formulation of the white pastes

The white pastes are formulated as follows (data in% by weight): 16.4 water 12.3 Additive solution, 40% 1.0 Defoamer (e.g. Tego Foamex LA-E 455, Tego Chemie Service GmbH) 70.0 Titanium dioxide 2160 (Kronos) 0.3 Aerosil A 200 (Degussa)

Formulation of the black pastes

The black pastes are formulated as follows (figures in% by weight): 60.3 water 22.3 Additive solution, 40% 1.0 Defoamer (e.g. Tego Foamex LA-E 455, Tego Chemie Service GmbH) 1.4 AMP 90 (Angus) 15.0 Color black FW 200 (Degussa)

Formulation of the red pastes

The red pastes are formulated as follows (figures in% by weight): 57.0 water 18.0 Additive solution, 40% 1.0 Defoamer (e.g. Tego Foamex LA-E 455, Tego Chemie Service GmbH) 24.0 Paliogen red 3885 (BASF)

Formulation of the blue pastes

The blue pastes are formulated as follows (figures in% by weight): 29.0 water 35.0 Additive solution, 40% 1.0 Defoamer (e.g. Tego Foamex LA-E 455, Tego Chemie Service GmbH) 35.0 Heliogen blue 7101 (BASF)

Test Coating Dispersion clear coat A

97.0

Neocryl XK 90 (Zeneca)

3.0

Texanol (Eastman)

Dispersion clear coat B

100.0

Daotan VTW 1225 (Clariant)

40.0 g each are used to produce mixed pigmented lacquers Submitted clear varnish, white paste and colored paste in the ratio 25: 1 (firm to firm) added and manually for 3 minutes homogenized with a brush. The samples are 100 µm Wet film thickness doctored on contrast cards and at room temperature dried (dispersion varnish).

Paste stability test:

To determine the paste stabilities, two different Shear rate (20 1 / s and 1000 1 / s) the achievable Initial viscosities as well as the viscosities after four weeks storage at 50 ° C determined.

White pastes

sample Viscosity / Pas immediately at 20 l / s Viscosity / Pas immediately at 1000 l / s Viscosity / Pas after 4 weeks 50 ° C at 20 / ls Viscosity / Pas after 4 weeks 50 ° C at 1000 l / s 1 0.64 0.18 0.82 0.30 2 0.58 0.17 0.73 00:29 3 0.53 0.15 0.72 0.30 4 0.61 0.19 0.69 0.27 5 0.65 0.15 0.77 0.34 6 0.79 0.12 1.46 0.58 7 0.72 0.15 1.23 0.53 8th 0.75 0.18 1.62 0.48

black pastes

sample Viscosity / dPas immediately at 20 l / s Viscosity / dPas immediately at 1000 l / s Viscosity / dPas after 4 weeks 50 ° C at 20 l / s Viscosity / dPas after 4 weeks 50 ° C at 1000 l / s 1 0.58 0.33 0.79 0.40 2 0.62 0.34 0.77 0.50 3 0.65 0.29 0.72 0.48 4 0.55 0.31 0.79 0.49 5 0.59 0.29 0.78 0.50 6 0.72 0.29 1.24 0.53 7 0.77 0.31 1.30 0.56 8th 0.81 0.33 1.33 0.60

Rotpasten

sample Viscosity / dPas immediately at 20 l / s Viscosity / dPas immediately at 1000 l / s Viscosity / dPas after 4 weeks 50 ° C at 20 l / s Viscosity / dPas after 4 weeks 50 ° C at 1000 l / s 1 0.62 0.40 0.75 0.73 2 0.58 0.37 0.80 00:59 3 0.64 0.48 0.79 0.61 4 0.66 0.49 0.90 0.70 5 0.56 0.42 0.70 0.60 6 0.84 0.39 1.54 0.86 7 0.91 0.54 1.58 0.79 8th 0.88 0.49 1.62 0.84

blue pastes

sample Viscosity / dPas immediately at 20 l / s Viscosity / dPas immediately at 1000 l / s Viscosity / dPas after 4 weeks 50 ° C at 20 l / s Viscosity / dPas after 4 weeks 50 ° C at 1000 l / s 1 0.54 0.36 0.70 0.49 2 0.56 0.29 0.59 0.41 3 0.49 0.31 0.65 0.45 4 0.59 0.41 0.74 0.55 5 0.50 0.33 0.57 0.44 6 0.84 0.29 1.39 0.86 7 0.83 0.31 1.42 0.91 8th 0.91 0.39 1.36 0.90

The only slight increase in viscosity can be seen the good stability of the pigment pastes according to the invention easy to recognize.

Dispersion test

The test formulations are applied with a 100 µm wet film thickness; after drying for six minutes, a rub-out test is carried out on 1/3 of the coated surface. After drying over Colorimetric takes place every 24 hours at night Measurement of the elevators using a spectrophotometer Type XP 68 from X-Rite. The determinations of gloss level and veils are made using the Haze-Gloss device Byk-Gardner company.

Dispersion varnish based on Neocryl XK 90 (gray)

sample Brightness L Delta E after rub-out Degree of gloss (60 ° angle) Haze 1 44.62 0.31 74.5 135 2 45.87 0.89 75.9 120 3 42.61 0.54 75.7 128 4 45.44 0.68 72.7 118 5 45.86 0.72 73.7 132 6 49.42 2.13 70.1 196 7 50.41 1.67 68.1 172 8th 54.66 1.39 69.9 268

Dispersion varnish based on Neocryl XK 90 (blue)

sample -b Delta E after rub-out Degree of gloss (60 ° angle) Haze 1 33.66 0.49 73.1 131 2 33.92 0.93 77.2 145 3 33,31 0.79 75.6 141 4 31.58 0.90 76.7 149 5 32,70 0.83 74.5 151 6 34.33 1.45 70.7 168 7 34.01 1.39 40.0 201 8th 34,75 1.79 71.0 170

Dispersion varnish based on Daotan VTW 1225 (gray)

sample Brightness L Delta E after rub-out Degree of gloss (60 ° angle) Haze 1 39.62 1.79 74.2 201 2 44.81 1.89 77.5 274 3 37.33 1.97 74.7 196 4 40,50 1.76 75.9 244 5 43.44 1.60 73.4 238 6 48.75 6.08 65.3 368 7 49,30 3.29 59.9 318 8th 46.12 5.65 61.2 322

Dispersion varnish based on Daotan VTW 1225 (blue)

sample -b Delta E after rub-out Degree of gloss (60 ° angle) Haze 1 35.67 2.72 78.8 157 2 36.76 2.37 78.4 144 3 37.27 3.14 80.2 165 4 35.89 1.95 81.1 182 5 35,79 2.89 79.3 153 6 41.79 7.92 48.3 232 7 42.04 6.18 72.7 215 8th 40.32 6.54 58.7 207

This can be seen through the use of dispersing additives achievable cheaper color strength development and the in all cases cheap rub-out test, caused by the additional polymer anchorage of the amine oxide groups the pigment surface.

As can be seen from the previous comparisons, are distinguished by their compounds universal applicability, the ease of manufacture more stable Pigment pastes, achievable levels of pigmentation, achievable Color stability and its very universal Use from.

Claims (8)

1. Maleic anhydride copolymers containing amine oxide groups, which are obtainable by reacting at least 1 mol% of the anhydride groups of maleic anhydride copolymers with

   a) diamines from the group consisting of HR¹N-R²-NR³R⁴    where

   R¹

   is hydrogen or a monovalent hydrocarbon radical having 1 to 24 carbon atoms,

   R²

   is a divalent alkylene radical having 2 to 24 carbon atoms, and

   R³ and R⁴

   are aliphatic and/or alicyclic alkyl radicals having 1 to 12, preferably 1 to 6, carbon atoms, which can be identical or different

   and subsequently carrying out oxidation to give amine oxide groups of the following general formula

   

   reacting some or all of the remaining anhydride groups with

   b) saturated or unsaturated, alicyclic or cyclic alcohols and/or amines of the general formula HO-R¹ or HR²N-R¹, respectively,
      where

   R¹

   is a hydrocarbon radical having 2 to 24 carbon atoms, and

   R²

   is hydrogen or a monovalent hydrocarbon radical having 1 to 24 carbon atoms,

   and/or

   c) polyoxyalkylene compounds of the general formula H- (O-C₂H_4-aR³ _a)_b(O-C_cH_2c)_dO-R⁴,    where

   R³

   are identical or different alkyl radicals or alkylene radicals having 1 to 24 carbon atoms or are substituted or unsubstituted phenyl radicals having up to 24 carbon atoms, and

   R⁴

   is hydrogen or a saturated or unsaturated, optionally branched or cyclic or aromatic hydrocarbon radical having up to 24 carbon atoms, which can, if desired, also include heteroatoms from the group consisting of O, S, N, P, Si, F, Cl, Br, and I,

   a = 0 to 3,
   b = 0 to 100,
   c = 2 to 12,
   d = 0 to 100,
   and the sum (b + d) = 2 to 200,
   the sequence of the polyoxyalkylene segments
   (O-C₂H_4-aR³ _a)_b and (O-C_cH_2c)_d being arbitrary,
   and/or

   d) polyoxyalkylene compounds of the general formula H₂N-R⁵-(O-C₂H_4-aR³ _a)_b(O-C_cH_2c)_dO-R⁶,

      where

   R³

   are identical or different alkyl radicals or alkylene radicals having 1 to 24 carbon atoms or are substituted or unsubstituted phenyl radicals having up to 24 carbon atoms,

   R⁵

   is a divalent alkylene radical having 2 to 6 carbon atoms, and

   R⁶

   is hydrogen or a saturated or unsaturated, optionally branched or cyclic or aromatic hydrocarbon radical having up to 24 carbon atoms, which can, if desired, also include heteroatoms from the group consisting of O, S, N, P, Si, F, Cl, Br, and I,

   a = 0 to 3,
   b = 0 to 100,
   c = 2 to 12,
   d = 0 to 100,
      and the sum (b + d) = 2 to 200,
      the sequence of the polyoxyalkylene segments (O-C₂H_4-aR³ _a)_b and (O-C_cH_2c)_d being arbitrary.
2. Maleic anhydride copolymers containing amine oxide groups according to Claim 1, characterized in that the polymer comprises as comonomer at least one further, different monomer having vinylic double bonds, preferably a monomer selected from the group consisting of styrene, alkylated styrene compounds, (meth)acrylic acid, (meth)acrylic esters, alkyl vinyl ethers, vinyl acetate, and itaconic esters or mixtures of monomers from this group.
3. Maleic anhydride copolymers containing amine oxide groups according to Claim 2, characterized in that styrene is used as comonomer and the molar ratio of maleic anhydride to styrene is between 1:1 and 1:3.
4. Maleic anhydride copolymers containing amine oxide groups according to Claims 1 to 3, characterized in that it has a weight-based molecular weight M_w of from 1000 to 100,000, preferably from 2500 to 50,000, g/mol.
5. Maleic anhydride copolymers containing amine oxide groups according to Claims 1 to 4, characterized in that carboxylic acid groups present in the polymer have been neutralized to carboxylate salts.
6. Use of the maleic anhydride copolymers containing amine oxide groups according to Claims 1 to 5 as a dispersant for pigments or fillers.
7. Use of the maleic anhydride copolymers containing amine oxide groups according to Claims 1 to 5 for preparing pigment concentrates, the dispersant being homogenized together with the pigments and/or fillers to be dispersed, if desired in the presence of organic solvents and/or water, if desired with binders and, if desired, with customary coating auxiliaries.
8. Use of the maleic anhydride copolymers containing amine oxide groups according to Claims 1 to 5 for preparing a coating composition, a binder being dispersed together, if desired, with a solvent, with pigments and/or fillers, with the dispersant and, if desired, with auxiliaries.